Aqueous photoprotective compositions comprising acrylamido-2-methylpropanesulfonic acid polymers and 4,4-diarylbutadiene UV-A sunscreens

ABSTRACT

Photoprotective compositions, e.g., oil-in-water or water-in-oil emulsions, well suited for the photoprotection of the skin, lips and/or hair against the damaging effects of UV-radiation, comprise at least one aqueous phase, at least one oily phase, at least one partially or completely neutralized, crosslinked or non-crosslinked water-soluble or water-dispersible acrylamido-2-methylpropanesulfonic acid (AMPS) polymer and at least one UV radiation-screening system, said at least one screening system comprising at least one 4,4-diarylbutadiene UV-A-screening agent

CROSS-REFERENCE TO PRIORITY/PROVISIONAL APPLICATIONS

[0001] This application claims priority under 35 U.S.C. § 119 of FR03/04647, filed Apr. 14, 2003, and of provisional application Serial No.60/468,089, filed May 6, 2003, both hereby expressly incorporated byreference and both assigned to the assignee hereof. This application isalso a continuation of said '089 provisional.

BACKGROUND OF THE INVENTION

[0002] 1. Technical Field of the Invention

[0003] The present invention relates to photoprotective compositionscomprising at least one aqueous phase, at least one oily phase, at leastone water-soluble or water-dispersible, partially or completelyneutralized, crosslinked or non-crosslinkedacrylamido-2-methylpropanesulfonic acid polymer and at least one UVradiation-screening system, which screening system comprises at leastone UV-A-screening agent of the 4,4-diarylbutadiene type.

[0004] 2. Description of Background and/or Related and/or Prior Art

[0005] It is well known that light radiation having wavelengths ofbetween 280 nm and 400 nm allows tanning of the human epidermis, andthat rays having wavelengths of between 280 nm and 320 nm, known by thename UV-B, cause erythemas and skin burns which can hamper thedevelopment of the natural tan; this UV-B radiation must therefore bescreened out.

[0006] It is also known that UV-A rays having wavelengths of between 320nm and 400 nm, which cause tanning of the skin, are capable of inducingits impairment, in particular in the case of a sensitive skin or a skincontinually exposed to solar radiation. UV-A rays cause in particular aloss of elasticity of the skin and the appearance of wrinkles which leadto premature aging. They promote the onset of the erythematous reactionor amplify this reaction in some subjects and may even be responsiblefor phototoxic or photoallergic reactions. It is therefore desirable toalso screen out UV-A radiation.

[0007] UV-A and UV-B rays must therefore be screened out and protectivecosmetic compositions for the human epidermis containing UV-A and UV-Bscreening agents currently exist.

[0008] These anti-sun compositions are often provided in the form of anemulsion of the oil-in-water type (that is to say a cosmetically and/ordermatologically acceptable carrier consisting of an aqueous dispersivecontinuous phase and a fatty dispersed discontinuous phase) or of thewater-in-oil type (aqueous phase dispersed in a continuous fatty phase),which contains, in various concentrations, one or more conventionalfat-soluble organic screening agents and/or conventional water solubleorganic screening agents capable of selectively absorbing harmful UVradiation, these screening agents (and their quantities) being selectedaccording to the desired sun protection factor, the sun protectionfactor (SPF) being mathematically expressed by the ratio of the dose ofUV radiation necessary to reach the erythematogenic threshold with theUV-screening agent to the dose of UV radiation necessary to reach theerythematogenic threshold without UV-screening agent. In such emulsions,the hydrophilic screening agents are present in the aqueous phase andthe lipophilic screening agents are present in the fatty phase.

[0009] Acrylamido-2-methylpropanesulfonic acid (AMPS) polymers areparticularly suited for their cosmetic properties and their flexibilityin terms of formulation, compared with the polymeric derivatives of thecarboxylic acid (Carbopols supplied by Noveon). They may indeed beformulated at pH values of between 4 and 6 without their gellingproperties being reduced. Among these derivatives, two large familiesmay be mentioned:

[0010] (a) the hydrophilic or water-dispersible polymers such asneutralized and crosslinked polyacrylamido-2-methylpropanesulfonic acidsupplied by Clariant under the name Hostacerin AMPS, or the copolymersof AMPS and other hydrophilic monomer(s) such as Sepigel 305 supplied bySEPPIC and Aristoflex AVC supplied by Clariant;

[0011] (b) the amphiphilic polymers comprising AMPS and alkyl recurringunits such as those described in EP-1,069,142.

[0012] These acrylamido-2-methylpropanesulfonic acid polymers areparticularly suitable in the manufacture of emulsions. They make itpossible to obtain stable formulations within a broad range of textureand consistency ranging from milks to thickened creams.

[0013] Among the organic UV-A-screening agents available, a family ofcompounds which are particularly effective in the UV-A region is1,4-benzene[di(3-methylidene-10-camphorsulfonic)]acid and its varioussalts, described in particular in FR-A-2,528,420 and FR-A-2,639,347;they are indeed capable of absorbing ultraviolet rays having wavelengthsof between 280 nm and 400 nm, with absorption maxima of between 320 nmand 400 nm, in particular in the region of 345 nm.

[0014] However, the introduction of this type of UV-A-screening agentinto photoprotective emulsions stabilized and/or thickened with anacrylamido-2-methylpropanesulfonic acid polymer can lead to asignificant reduction in their viscosity or to their destabilization.

[0015] It thus appears necessary to have emulsions based onacrylamido-2-methylpropanesulfonic acid polymers which are stable andwhich may contain organic screening agents which are active in UV-A withcomparable efficacy to that of1,4-benzene[di(3-methylidene-10-camphorsulfonic)]acid and its differentsalts without the disadvantages listed above.

[0016] The expression “stable” is understood to mean that themacroscopic and microscopic appearance of the composition is notmodified after 1 month at room temperature.

SUMMARY OF THE INVENTION

[0017] It has now surprisingly and unexpectedly been determined thatemulsions comprising at least one partially or completely neutralized,crosslinked or non-crosslinked acrylamido-2-methylpropanesulfonic acidpolymer and at least one UV-A-screening agent of the 4,4-diarylbutadienetype ameliorate or avoid those disadvantages and drawbacks indicatedabove.

[0018] In the remainder of the present description, the expression “UVradiation-screening system” is understood to mean a UVradiation-screening agent comprising either a single organic orinorganic compound screening out UV radiation or a mixture of severalorganic or inorganic compounds screening out UV radiation, for example amixture comprising a UV-A-screening agent and a UV-B-screening agent.

[0019] This discovery forms the basis of the present invention.

[0020] Thus, the present invention features photoprotective compositionscomprising at least one aqueous phase, at least one oily phase, at leastone partially or completely neutralized, crosslinked or non-crosslinkedwater-soluble or water-dispersible acrylamido-2-methylpropanesulfonicacid polymer and at least one UV radiation-screening system, whichscreening system comprises at least one UV-A-screening agent of the4,4-diarylbutadiene type.

[0021] Other characteristics, aspects and advantages of the inventionwill be seen from the detailed description which follows.

DETAILED DESCRIPTION OF BEST MODE AND SPECIFIC/PREFERRED EMBODIMENTS OFTHE INVENTION

[0022] The polymers formulated in accordance with the invention arecrosslinked or non-crosslinked homopolymers or copolymers containing atleast the acrylamido-2-methylpropanesulfonic acid (AMPS) monomer, infree or alternatively partially or completely neutralized form.

[0023] Preferably, the AMPS polymers in accordance with the inventionmay be partially or completely neutralized with an inorganic base(sodium hydroxide, potassium hydroxide, aqueous ammonia) or an organicbase such as mono-, di- or triethanolamine, an aminomethypropanediol,N-methylglucamine, basic amino acids such as arginine and lysine, andmixtures of these compounds. They are generally neutralized. Theexpression “neutralized” is understood to mean in the present inventionpolymers which are completely or practically completely neutralized,that is to say at least 90% neutralized.

[0024] These AMPS polymers according to the invention may be crosslinkedor non-crosslinked.

[0025] When the polymers are crosslinked, the crosslinking agents may beselected from among the olefinically polyunsaturated compounds commonlyused for the crosslinking of polymers obtained by free-radicalpolymerization.

[0026] There may be mentioned, for example, as crosslinking agents,divinylbenzene, diallyl ether, dipropylene glycol diallyl ether,polyglycol diallyl ethers, triethylene glycol divinyl ether,hydroquinone diallyl ether, ethylene glycol or tetraethylene glycoldi(meth)acrylate, trimethylol propane triacrylate,methylenebisacrylamide, methylenebismethacrylamide, triallylamine,triallyl cyanurate, diallyl maleate, tetraallylethylenediamine,tetraallyloxyethane, trimethylolpropane diallyl ether,allyl(meth)acrylate, allyl ethers of alcohols of the sugar series, orother allyl or vinyl ethers of polyfunctional alcohols, and the allylesters of phosphoric and/or vinylphosphonic acid derivatives, ormixtures of these compounds.

[0027] According to a preferred embodiment of the invention, thecrosslinking agent is selected from methylenebisacrylamide, allylmethacrylate or trimethylolpropane triacrylate (TMPTA). The degree ofcrosslinking ranges in general from 0.01 mol % to 10 mol % and moreparticularly from 0.2 mol % to 2 mol % relative to the polymer.

[0028] The AMPS polymers in accordance with the invention may bewater-soluble or water-dispersible. They are in this case:

[0029] either “homopolymers” containing only AMPS monomers and, if theyare crosslinked, one or more crosslinking agents such as those definedabove;

[0030] or copolymers obtained from AMPS and one or more hydrophilic orhydrophobic ethylenically unsaturated monomers and, if they arecrosslinked, one or more crosslinking agents such as those definedabove. When the said copolymers contain hydrophobic ethylenicallyunsaturated monomers, the latter do not contain a fatty chain and arepreferably present in small quantities.

[0031] The expression “fatty chain” is understood to mean, for thepurposes of the present invention, any hydrocarbon chain containing atleast 7 carbon atoms.

[0032] The expression “water-soluble or water-dispersible” is understoodto mean polymers which, when introduced into an aqueous phase at 25° C.,at a concentration by mass equal to 1%, allow the obtaining of amacroscopically homogeneous and transparent solution, that is to sayhaving a maximum light transmittance value, at a wavelength equal to 500nm, through a sample 1 cm thick, of at least 60%, preferably of at least70%.

[0033] The AMPS polymers in accordance with the invention may also beamphiphilic, namely that they contain both a hydrophilic part or moietyand a hydrophobic part or moiety containing at least one fatty chain.

[0034] Water-Soluble or Water-Dispersible Polymers:

[0035] When the polymers in accordance with the invention arewater-soluble or water-dispersible (non-amphiphilic) copolymers, theyare:

[0036] either “homopolymers” containing only AMPS monomers and, if theyare crosslinked, one or more crosslinking agents;

[0037] or copolymers obtained from AMPS and one or more hydrophilic orhydrophobic ethylenically unsaturated monomers and, if they arecrosslinked, one or more crosslinking agents. When the said copolymerscontain hydrophobic ethylenically unsaturated monomers, the latter donot contain a fatty chain (number of carbon atoms not exceeding 6).

[0038] The “homopolymers” according to the invention are preferablycrosslinked and neutralized, and they may be obtained according to themethod of preparation comprising the following steps:

[0039] (a) the monomer such as AMPS in free form is dispersed ordissolved in a solution of tert-butanol or of water and tert-butanol;

[0040] (b) the solution or dispersion of monomer obtained in (a) isneutralized with one or more inorganic or organic bases, preferablyaqueous ammonia NH₃, in a quantity which makes it possible to obtain adegree of neutralization of the sulfonic acid functional groups of thepolymer ranging from 90% to 100%;

[0041] (c) the crosslinking monomer(s) is(are) added to the solution ordispersion obtained in (b);

[0042] (d) a conventional free-radical polymerization is carried out inthe presence of free radical initiators at a temperature ranging from 10to 150° C.; the polymer precipitating in the solution or the dispersionbased on tert-butanol.

[0043] As polymers of this type, there may be mentioned, in particular,the crosslinked and neutralized 2-acrylamido-2-methylpropanesulfonicacid homopolymer marketed by Hoechst under the trademark “HostacerinAMPS” (CTFA name: ammonium polyacryldimethyltauramide).

[0044] The water-soluble or water-dispersible AMPS copolymers accordingto the invention contain water-soluble, ethylenically unsaturatedmonomers, hydrophobic monomers or mixtures thereof.

[0045] The water-soluble comonomers may be ionic or nonionic.

[0046] Among the ionic water-soluble comonomers, there may be mentioned,for example the following compounds and their salts:

[0047] (meth)acrylic acid,

[0048] styrenesulfonic acid,

[0049] vinylsulfonic acid and (meth)allylsulfonic acid,

[0050] vinylphosphonic acid,

[0051] maleic acid,

[0052] itaconic acid,

[0053] crotonic acid,

[0054] dimethyldiallylammonium chloride,

[0055] methylvinylimidazolium chloride,

[0056] ethylenic carboxybetaines or sulfobetaines obtained for exampleby quaternization of ethylenically unsaturated monomers containing anamine functional group, with sodium salts of a carboxylic acid with anactive halogen (e.g.,: chloroacetate) or with cyclic sulfones (e.g.,:propanesulfone),

[0057] water-soluble vinyl monomers of the following formula (A):

[0058] in which R₁ is selected from H, —CH₃, —C₂H₅ or —C₃H₇ and X₁ isselected from the group consisting of:

[0059] alkyl oxides of the —OR₂ type wherein R₂ is a saturated orunsaturated, linear or branched hydrocarbon radical having from 1 to 6carbon atoms, substituted with at least one sulfonic group (—SO₃—)and/or sulfate group (—SO₄—) and/or phosphate group (—PO₄H₂—) and/orquaternary ammonium group (—N⁺R₃R₄R₅) in which R₃, R₄ and R₅, which maybe identical or different, are each a saturated or unsaturated, linearor branched hydrocarbon radical having 1 to 6 carbon atoms, providedthat the sum of the carbon atoms of R₁+R₂+R₃+R₄ does not exceed 6. Theradical R₁ is optionally substituted with a halogen atom (iodine,bromine, chlorine, fluorine); a hydroxyl (—OH); an ether (—O—), aprimary amine (—NH₂); a secondary amine (—NHR₆), a tertiary amine(—NR₆R₇) in which R₆ and R₇, which may be identical or different, areeach a saturated or unsaturated, linear or branched hydrocarbon radicalhaving 1 to 6 carbon atoms, provided that the sum of the carbon atoms ofR₂+R₆+R₇ does not exceed 6. Exemplary is quaternized dimethylaminoethylmethacrylate (DAMEMA).

[0060] —NH₂, —NHR₈ and —NR₈R₉ groups in which R₈ and R₉, which may beidentical or different, are each a saturated or unsaturated, linear orbranched hydrocarbon radical having 1 to 6 carbon atoms, provided thatthe total number of carbon atoms of R₈+R₉ does not exceed 6, the said R₈and/or R₉ being substituted with at least one sulfonic group (—SO₃—)and/or sulfate group (—SO₄—) and/or phosphate group (—PO₄H₂—) and/orquaternary amine group (—N⁺R₁₀R₁₁R₁₂) in which R₁₀, R₁₁ and R₁₂, whichmay be identical or different, are each a saturated or unsaturated,linear or branched hydrocarbon radical having 1 to 6 carbon atoms,provided that the number of carbon atoms of R₈+R₉+R₁₀+R₁₁+R₁₂ does notexceed 6. The radicals R₈ and/or R₉ are optionally substituted with ahalogen atom (iodine, bromine, chlorine, fluorine); a hydroxyl group(—OH); an ether group (—O—), a primary amine group (—NH₂); a secondaryamine group (—NHR₁₃), a tertiary amine group (—NR₁₃R₁₄) in which R₁₃ andR₁₄, which may be identical or different, are each a saturated orunsaturated, linear or branched hydrocarbon radical having 1 to 6 carbonatoms, provided that the sum of the carbon atoms of R₈+R₉+R₁₃+R₁₄ doesnot exceed 6. Exemplary is (meth)acrylamidopropyltrimethylammoniumchloride (APTAC and MAPTAC).

[0061] Among the nonionic water-soluble comonomers, there may bementioned, for example:

[0062] (meth)acrylamide,

[0063] N-vinylacetamide and N-methyl-N-vinylacetamide,

[0064] N-vinylformamide and N-methyl-N-vinylformamide,

[0065] maleic anhydride,

[0066] vinylamine,

[0067] N-vinyllactams containing a cyclic alkyl group having from 4 to 9carbon atoms, such as N-vinylpyrrolidone, N-butyrolactam andN-vinylcaprolactam,

[0068] vinyl alcohol of formula CH₂═CHOH,

[0069] water-soluble vinyl monomers of the following formula (B):

[0070] in which R₁₅ is selected from H, —CH₃, —C₂H₅ or —C₃H₇ and X₂ isselected from the group consisting of:

[0071] alkyl oxides of the —OR₁₆ type wherein R₁₆ is a saturated orunsaturated, linear or branched hydrocarbon radical having from 1 to 6carbons, optionally substituted with a halogen atom (iodine, bromine,chlorine, fluorine); a hydroxyl group (—OH); an ether group (—O—), aprimary amine group (—NH₂); a secondary amine group (—NHR₁₇), a tertiaryamine group (—NR₁₇R₁₈) in which R₁₇ and R₁₈, which may be identical ordifferent, are each a saturated or unsaturated, linear or branchedhydrocarbon radical having 1 to 6 carbon atoms, provided that the sum ofthe carbon atoms of R₁₆+R₁₇+R₁₈ does not exceed 6. Exemplary is glycidyl(meth)acrylate, hydroxyethyl methacrylate, and ethylene glycol,diethylene glycol or polyalkylene glycol (meth)acrylates;

[0072] —NH₂, —NHR₁₉ and —NR₁₉R₂₀ groups in which R₁₉ and R₂₀, which maybe identical or different, are each a saturated or unsaturated, linearor branched hydrocarbon radical having 1 to 6 carbon atoms, providedthat the total number of carbon atoms of R₁₉+R₂₀ does not exceed 6, thesaid R₁₉ and R₂₀ being optionally substituted with a halogen atom(iodine, bromine, chlorine, fluorine); a hydroxyl group (—OH); an ethergroup (—O—); a primary amine group (—NH₂); a secondary amine group(—NHR₂₁), a tertiary amine group (—NR₂₁R₂₂) in which R₂₁ and R₂₂, whichmay be identical or different, are each a saturated or unsaturated,linear or branched hydrocarbon radical having 1 to 6 carbon atoms,provided that the sum of the carbon atoms of R₁₉+R₂₀+R₂₁+R₂₂ does notexceed 6. Exemplary is dimethylaminoethylmethacrylamide.

[0073] Among the hydrophobic comonomers with no fatty chain, there maybe mentioned, for example:

[0074] styrene and its derivatives such as 4-butylstyrene,alpha-methylstyrene and vinyltoluene,

[0075] vinyl acetate of formula CH₂═CH—OCOCH₃,

[0076] vinyl ethers of formula CH₂═CHOR in which R is a saturated orunsaturated, linear or branched hydrocarbon radical having from 1 to 6carbons,

[0077] acrylonitrile,

[0078] caprolactone,

[0079] vinyl chloride and vinylidene chloride,

[0080] silicone derivatives, after polymerization providing siliconepolymers such as methacryloxypropyltris(trimethylsiloxy)silane andsilicone methacrylamides,

[0081] hydrophobic vinyl monomers of the following formula (C):

[0082] in which R₂₃ is selected from H, —CH₃, —C₂H₅ or —C₃H₇ and X₃ isselected from the group consisting of:

[0083] alkyl oxides of the —OR₂₄ type where R₂₄ is a saturated orunsaturated, linear or branched hydrocarbon radical having from 1 to 6carbon atoms;

[0084] —NH₂, —NHR₂₅ and —NR₂₅R₂₆ groups in which R₂₅ and R₂₆, which maybe identical or different, are each a saturated or unsaturated, linearor branched hydrocarbon radicals having 1 to 6 carbon atoms, providedthat the total number of carbon atoms of R₂₅+R₂₆ does not exceed 6.Exemplary are methyl methacrylate, ethyl methacrylate,n-butyl(meth)acrylate, tert-butyl(meth)acrylate, cyclohexyl acrylate,isobornyl acrylate and 2-ethylhexyl acrylate.

[0085] The water-soluble or water-dispersible AMPS polymers of theinvention preferably have a molar mass ranging from 50,000 g/mol to10,000,000 g/mol, preferably from 80,000 g/mol to 8,000,000 g/mol, andmore preferably still from 100,000 g/mol to 7,000,000 g/mol.

[0086] As water-soluble or water-dispersible copolymers obtained fromAMPS and ethylenically unsaturated water-soluble monomers, there may bementioned, for example, those obtained from AMPS and acrylamide ormethacrylamide, such as, for example, the acrylamide/sodiumacrylamido-2-methylpropanesulfonate crosslinked copolymer as an emulsionin C₁₃-C₁₄ isoparaffin and laureth-7 (CTFA name: Polyacrylamide/C₁₃-C₁₄isoparaffin/laureth-7) marketed under the name SEPIGEL 305 oracrylamide/sodium acrylamido-2-methylpropanesulfonate crosslinkedcopolymer as an invert emulsion at 40% in isohexadecane andpolysorbate-80 (CTFA name: Acrylamide/SodiumAcryloyldimethyltaurate/isohexadecane/polysorbate-80) marketed under thename SIMULGEL 600 by SEPPIC. There may also be mentioned the copolymersof AMPS and vinylpyrrolidone or vinylformamide, such as the productsammonium acryloyldimethyltaurate/VP copolymer (INCI name) marketed underthe name ARISTOFLEX AVC by CLARIANT. There may also be mentioned thecopolymers of AMPS and sodium acrylate, such as for example AMPS/sodiumacrylate crosslinked copolymer as an invert emulsion in awater/isohexadecane/sorbitan oleate mixture (CTFA name:Acrylamide/Sodium Acryloyldimethyltaurate/Isohexadecane/polysorbate-80)marketed under the name SIMULGEL EG by SEPPIC. There may also bementioned the copolymers of AMPS and hydroxyethyl acrylate, such as forexample AMPS/hydroxyethyl acrylate crosslinked copolymer as an invertemulsion in a polysorbate 60/squalane mixture (INCI name: Hydroxyethylacrylate/Sodium Acryloyldimethyltaurate copolymer (and) squalane (and)polysorbate 60) marketed under the name SIMULGEL NS by SEPPIC.

[0087] Amphiphilic AMPS Polymers:

[0088] The amphiphilic AMPS polymers in accordance with the inventioncontain both a hydrophilic part or moiety and a hydrophobic part ormoiety containing at least one fatty chain.

[0089] The fatty chain present in the polymers of the inventionpreferably contain from 7 to 30 carbon atoms, more preferably from 7 to22 carbon atoms and more preferably still from 7 to 18 atoms and moreparticularly from 12 to 18 carbon atoms.

[0090] The amphiphilic polymers in accordance with the invention have ingeneral a weight-average molecular weight ranging from 50,000 to10,000,000, more preferably from 100,000 to 8,000,000 and morepreferably still from 100,000 to 7,000,000.

[0091] The amphiphilic AMPS polymers according to the invention may becrosslinked or non-crosslinked. The crosslinking agents may be selectedfrom among those mentioned above. There may be used more particularlymethylenebisacrylamide, allyl methacrylate or trimethylolpropanetriacrylate (TMPTA). The degree of crosslinking preferably varies from0.01 mol % to 10 mol %, and more particularly from 0.2 mol % to 2 mol %relative to the polymer.

[0092] The amphiphilic AMPS polymers in accordance with the inventionmay be selected in particular from among random amphiphilic AMPSpolymers modified by reaction with a C₆-C₂₂ n-monoalkylamine ordi-n-alkylamine such as those described in WO 00/31154. These polymersmay also contain other ethylenically unsaturated hydrophilic monomersselected, for example, from among acrylic acid, methacrylic acid ortheir β-substituted alkyl derivatives or their esters obtained withmono- or polyalkylene glycols, acrylamide, methacrylamide,vinylpyrrolidone, itaconic acid, maleic acid or mixtures thereof.

[0093] The preferred polymers of the invention are selected from amongthe amphiphilic polymers of AMPS and at least one ethylenicallyunsaturated monomer containing at least one hydrophobic part or moietyhaving from 7 to 30 carbon atoms and more preferably from 7 to 22 carbonatoms and even more preferably still from 7 to 18 carbon atoms and moreparticularly from 12 to 18 carbon atoms. This hydrophobic part or moietymay be a saturated or unsaturated, linear alkyl radical (for examplen-octyl, n-decyl, n-hexadecyl, n-dodecyl, oleyl), branched radical (forexample isostearyl) or cyclic radical (for example cyclododecane oradamantane).

[0094] These same polymers may further contain one or more ethylenicallyunsaturated hydrophilic comonomers such as acrylic acid, methacrylicacid or their β-substituted alkyl derivatives or their esters obtainedwith mono- or polyalkylene glycols, acrylamide, methacrylamide,vinylpyrrolidone, itaconic acid or maleic acid.

[0095] These same polymers may further contain one or more ethylenicallyunsaturated hydrophobic comonomers comprising, for example:

[0096] a C₇-C₁₈ fluorinated or alkylfluorinated radical (for example thegroup of formula —(CH₂)₂—(CF₂)₉—CF₃),

[0097] a cholesteryl radical or a radical derived from cholesterol (forexample cholesteryl hexanoate),

[0098] an aromatic polycyclic group such as naphthalene or pyrene,

[0099] a silicone or alkylsilcone or alternatively alkylfluorosiliconeradical.

[0100] These copolymers are described in particular in EP-A-750,899, inU.S. Pat. No. 5,089,578 and in the following publications by YotaroMorishima:

[0101] “Self-assembling amphiphilic polyelectrolytes and theirnanostructures—Chinese Journal of Polymer Science, Vol. 18, No. 40,(2000), 323-336;

[0102] “Micelle formation of random copolymers of sodium2-(acrylamido-2-methylpropanesulfonate and a non-ionic surfactantmacromonomer in water as studied by fluorescence and dynamic lightscattering—Macromolecules 2000, Vol. 33, No. 10-3694-3704”;

[0103] “Solution properties of miscelle networks formed by non-ionicmoieties covalently bound to an polyelectrolyte: salt effects onrheological behaviour—Langmuir, 2000, Vol. 16, No. 12, 5324-5332”;

[0104] “Stimuli response amphiphilic copolymers of sodium2-(acrylamido)-2-methylpropanesulfonate and associativemacromonomers—Polym. Preprint, Div. Polym. Chem. 1999, 40(2), 220-221”.

[0105] They are also described in (CLARIANT): EP-1,069,142, WO 02/44224,WO 02/44225, WO 02/44227, WO 02/44229, WO 02/44230, WO 02/44231, WO02/44267, WO 02/44268, WO 02/44269, WO 02/44270, WO 02/44271, WO02/43677, WO 02/43686, WO 02/43687, WO 02/43688, WO 02/43689.

[0106] The ethylenically unsaturated hydrophobic monomers of theinvention are preferably selected from among the acrylates andacrylamides of the following formula (1):

[0107] in which R₂₇ is a hydrogen atom, a linear or branched C₁-C₆ alkylradical (preferably methyl); Y is O or NH; R₂₈ is a hydrophobic radicalcontaining a fatty chain having from 7 to 22 carbon atoms, andpreferably 7 to 18, and more particularly from 12 to 18 carbon atoms.

[0108] The hydrophobic radical R₂₈ is preferably selected from among thesaturated or unsaturated, linear C₇-C₁₈ alkyl radicals (for examplen-octyl, n-decyl, n-hexadecyl, n-dodecyl, oleyl), branched radicals (forexample isostearyl) or cyclic radicals (for example cyclododecane oradamantane); perfluorinated C₇-C₁₈ alkyl radicals (for example the groupof formula —(CH₂)₂—(CF₂)₉—CF₃); the cholesteryl radical or a cholesterolester such as cholesteryl hexanoate; aromatic polycyclic groups such asnaphthalene or pyrene. Among these radicals, the linear and branchedalkyl radicals are more particularly preferred.

[0109] According to a particularly preferred embodiment of theinvention, the hydrophobic radical R₂₈ further contains at least onealkylene oxide unit and preferably a polyoxyalkylenated chain. Thepreferably polyoxyalkylenated chain comprises ethylene oxide unitsand/or propylene oxide units and more particularly still solelycomprises ethylene oxide units. The number of moles of oxyalkylenatedunits varies in general from 1 to 30 mol and more preferably from 1 to25 mol and more preferably still from 3 to 20 mol.

[0110] Among these polymers, there may be mentioned:

[0111] neutralized or non-neutralized, crosslinked or non-crosslinkedcopolymers containing from 15% to 60% by weight of AMPS units and from40% to 85% by weight of (C₈-C₁₆)alkyl (meth)acrylamide units or(C₈-C₁₆)alkyl (meth)acrylate units relative to the polymer, such asthose described in EP-A-750,899;

[0112] terpolymers containing from 10 to 90 mol % of acrylamide units,from 0.1 to 10 mol % of AMPS units and from 5 to 80 mol % ofn-(C₆-C₁₈)alkyl acrylamide units, relative to the polymer, such as thosedescribed in U.S. Pat. No. 5,089,578.

[0113] As amphiphilic polymers, there may also be mentioned thecopolymers of completely neutralized AMPS and of n-dodecyl, n-hexadecyland/or n-octadecyl methacrylate, and the copolymers of AMPS andn-dodedcyl methacrylamide, which are non-crosslinked and crosslinked.

[0114] There may be mentioned, more particularly, the crosslinked ornon-crosslinked amphiphilic copolymers comprising:

[0115] (a) 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of thefollowing formula (2):

[0116] in which X⁺ is a proton, an alkali metal cation, an alkalineearth metal cation or the ammonium ion;

[0117] (b) and of units of the following formula (3):

[0118] in which n and p, which may be identical or different, denote anumber of moles and varies from 0 to 30, preferably from 1 to 25 andmore preferably from 3 to 20, provided that n+p is less than or equal to30, preferably less than 25 and better still less than 20; R₂₇ has thesame meaning indicated above in formula (1) and R₂₉ is a linear orbranched alkyl radical containing m carbon atoms ranging from 7 to 22,preferably from 7 to 18 carbon atoms and better still from 12 to 18carbon atoms.

[0119] In formula (2), the cation X⁺ more particularly is sodium orammonium.

[0120] Among the monomers of formula (3), there may be mentioned:

[0121] esters of (meth)acrylic acid and a polyoxyethylenated C₁₀-C₁₈fatty alcohol containing 8 EO such as the product GENAPOL C-080 sold byCLARIANT;

[0122] esters of (meth)acrylic acid and a polyoxyethylenated C₁₁ fattyoxoalcohol containing 8 EO such as the product GENAPOL UD-080 sold byCLARIANT;

[0123] esters of (meth)acrylic acid and a polyoxyethylenated C₁₂-C₁₄fatty alcohol containing 7 EO such as the product GENAPOL LA-070 sold byCLARIANT;

[0124] esters of (meth)acrylic acid and a polyoxyethylenated C₁₂-C₁₄fatty alcohol containing 11 EO such as the product GENAPOL LA-110 soldby CLARIANT;

[0125] esters of (meth)acrylic acid and a polyoxyethylenated C₁₆-C₁₈fatty alcohol containing 8 EO such as the product GENAPOL T-080 sold byCLARIANT;

[0126] esters of (meth)acrylic acid and a polyoxyethylenated C₁₆-C₁₈fatty alcohol containing 15 EO such as the product GENAPOL T-150 sold byCLARIANT;

[0127] esters of (meth)acrylic acid and a polyoxyethylenated C₁₆-C₁₈fatty alcohol containing 11 EO such as the product GENAPOL T-110 sold byCLARIANT;

[0128] esters of (meth)acrylic acid and a polyoxyethylenated C₁₆-C₁₈fatty alcohol containing 20 EO such as the product GENAPOL T-200 sold byCLARIANT;

[0129] esters of (meth)acrylic acid and a polyoxyethylenated C₁₆-C₁₈fatty alcohol containing 25 EO such as the product GENAPOL T-250 sold byCLARIANT;

[0130] esters of (meth)acrylic acid and a polyoxyethylenated C₁₈-C₂₂fatty alcohol containing 25 EO and/or a polyoxyethylenated C₁₆-C₁₈ fattyisoalcohol containing 25 EO.

[0131] There will more particularly be selected:

[0132] (i) those which are non-crosslinked, for which p=0, n=7 or 25,R₂₇ is methyl and R₂₉ is a mixture of C₁₂-C₁₄ or C₁₆-C₁₈ alkyl,

[0133] (ii) those which are crosslinked, for which p=0, n=8 or 25, R₂₇is methyl and R₂₉ represents a mixture of C₁₆-C₁₈ alkyl.

[0134] These polymers are described and synthesized in EP-1,069,142.These particular amphiphilic polymers may be obtained according toconventional free-radical polymerization methods in the presence of oneor more initiators such as for example azobisisobutyronitrile (AIBN),azobisdimethylvaleronitrile, 2,2-azobis[2-amidinopropane]hydrochloride(ABAH=2,2-azo-bis-[2-aminopropane]hydrochloride), organic peroxides suchas dilauryl peroxide, benzoyl peroxide, tert-butyl hydroperoxide, andthe like, inorganic peroxide compounds such as potassium or ammoniumpersulfate, or H₂O₂ optionally in the presence of reducing agents.

[0135] These amphiphilic polymers may be obtained in particular byfree-radical polymerization in a tert-butanol medium in which theyprecipitate. Using polymerization by precipitation in tert-butanol, itis possible to obtain a distribution of the size of the polymerparticles which is particularly favorable for its uses.

[0136] The reaction may be performed at a temperature of between 0 and150° C., preferably between 10 and 100° C., or at atmospheric pressureor under reduced pressure. It may also be carried out under an inertatmosphere, preferably under nitrogen.

[0137] The polymers in accordance with the invention are preferablypartially or completely neutralized with an inorganic or organic basesuch as those described above.

[0138] The mol % concentration of the units of formula (2) and of theunits of formula (3) in the amphiphilic polymers according to theinvention varies according to the desired cosmetic application, thenature of the emulsion (oil-in-water or water-in-oil) and the desiredrheological properties of the formulation. They may vary between 0.1 and99.9 mol %.

[0139] The scarcely hydrophobic amphiphilic AMPS polymers according tothe invention will be more appropriate for thickening and/or stabilizingthe oil-in-water emulsions. The molar proportion of units of formula (3)will preferably vary from 0.1% to 50%, more particularly from 1% to 25%and more particularly still from 3% to 10%.

[0140] The more hydrophobic amphiphilic AMPS polymers according to theinvention will be more appropriate for thickening and/or stabilizing thewater-in-oil emulsions. The molar proportion of units of formula (3)will preferably vary from 50.1% to 99.9%, more particularly from 60% to95% and more particularly still from 65% to 90%.

[0141] The distribution of the monomers in the polymers of the inventionmay be for example alternating, block (including multiblock) or of anytype.

[0142] The AMPS polymers in accordance with the invention are generallypresent in quantities as active material ranging from 0.01% to 20% byweight, more preferably from 0.1% to 10% by weight, still morepreferably from 0.1% to 5% by weight and more particularly still from0.5% to 2% by weight relative to the total weight of the composition.

[0143] The 4,4-diarylbutadiene compounds in accordance with theinvention are preferably selected from among those corresponding to thefollowing formula (I):

[0144] in which the diene system is of the Z,Z; Z,E; E,Z or E,Econfiguration or mixtures of the said configurations, and wherein:

[0145] R¹ and R², which may be identical or different, are eachhydrogen, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenyl radical, a C₁-C₁₂alkoxy radical, a C₃-C₁₀ cycloalkyl radical, a C₃-C₁₀ cycloalkenylradical, a C₁-C₂₀ alkoxycarbonyl radical, a C₁-C₁₂ monoalkylaminoradical, a C₁-C₁₂ dialkylamino radical, an aryl radical, a heteroarylradical or a water-solubilizing substituent selected from among acarboxylate residue, a sulfonate residue or an ammonium residue;

[0146] R³ is a group COOR⁵, COR⁵, CONR⁵R⁶, CN, O═S(—R⁵)═O, O═S(—OR⁵)═O,R⁷O—P—(—OR⁸)═O, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenyl radical, aC₃-C₁₀ cycloalkyl radical, a C₇-C₁₀ bicycloalkyl radical, a C₃-C₁₀cycloalkenyl radical, a C₇-C₁₀ bicycloalkenyl radical, an optionallysubstituted C₆-C₁₈ aryl radical, an optionally substituted C₃-C₇heteroaryl radical;

[0147] R⁴ is a group COOR⁶, COR⁶, CONR⁵R⁶, CN, O═S(—R⁶)═O, O═S(—OR⁶)═O,R⁷O—P—(—OR⁸)═O, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenyl radical, aC₃-C₁₀ cycloalkyl radical, a C₇-C₁₀ bicycloalkyl radical, a C₃-C₁₀cycloalkenyl radical, a C₇-C₁₀ bicycloalkenyl radical, an optionallysubstituted C₆-C₁₈ aryl radical, an optionally substituted C₃-C₇heteroaryl radical;

[0148] the radicals R⁵ to R⁸, which may be identical or different, areeach hydrogen, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenyl radical, aC₃-C₁₀ cycloalkyl radical, a C₇-C₁₀ bicycloalkyl radical, a C₃-C₁₀bicycloalkenyl radical, a C₇-C₁₀ cycloalkenyl radical, an optionallysubstituted aryl radical, an optionally substituted heteroaryl radical;and n ranges from 1 to 3; with the proviso that the radicals R³ to R⁸can together form, with the carbon atoms from which they depend, a C₅-C₆ring which may be fused.

[0149] As C₁-C₂₀ alkyl radicals, there may be mentioned, for example:methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl,n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl,n-nonadecyl or n-eicosyl.

[0150] As C₂-C₁₀ alkenyl groups, there may be mentioned, for example:ethenyl, n-propenyl, 1-methylethenyl, n-butenyl, 1-methylpropenyl,2-methylpropenyl, 1,1-dimethylethenyl, n-pentenyl, 1-methylbutenyl,2-methylbutenyl, 3-methylbutenyl, 2,2-dimethylpropenyl, 1-ethylpropenyl,n-hexenyl, 1,1-dimethylpropenyl, 1,2-dimethylpropenyl, 1-methylpentenyl,2-methylpentenyl, 3-methylpentenyl, 4-methylpentenyl,1,1-dimethylbutenyl, 1,2-dimethylbutenyl, 1,3-dimethylbutenyl,2,2-dimethylbutenyl, 2,3-dimethylbutenyl, 3,3-dimethylbutenyl,1-ethylbutenyl, 2-ethylbutenyl, 1,1,2-trimethylpropenyl,1,2,2-trimethylpropenyl, 1-ethyl-1-methylpropenyl,1-ethyl-2-methylpropenyl, n-heptenyl, n-octenyl, n-nonenyl, n-decenyl.

[0151] As C₁-C₁₂ alkoxy radicals, there may be mentioned: methoxy,n-propxy, 1-methylpropoxy, 1-methylethoxy, n-pentoxy, 3-methylbutoxy,2,2-dimethylpropoxy, 1-methyl-1-ethylpropoxy, octoxy, ethoxy, n-propoxy,n-butoxy, 2-methylpropoxy, 1,1-dimethylpropoxy, hexoxy, heptoxy,2-ethylhexoxy.

[0152] As C₁-C₂₀ alkoxycarbonyl radicals, there may be mentioned estersof C₁-C₂₀ alcohols.

[0153] As C₁-C₁₂ monoalkylamino or dialkylamino radicals, there may bementioned those in which the alkyl radical(s) is(are) selected fromamong methyl, n-propyl, 2-methylpropyl, 1,1-dimethylethyl, hexyl,heptyl, 2-ethylhexyl, isopropyl, 1-methylpropyl, n-pentyl,3-methylbutyl, 2,2-dimethylpropyl, 1-methyl-1-ethylpropyl, octyl.

[0154] As C₃-C₁₀ cycloalkyl radicals, there may be mentioned, forexample: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,1-methylcyclopropyl, 1-ethylcyclopropyl, 1-propylcyclopropyl,1-butylcyclopropyl, 1-pentylcyclopropyl, 1-methyl-1-butylcyclopropyl,1,2-dimethylcyclopropyl, 1-methyl-2-ethylcyclopropyl, cyclooctyl,cyclononyl or cyclodecyl.

[0155] As C₃-C₁₀ cycloalkenyl radicals having one or more double bonds,there may be mentioned: cyclobutenyl, cyclopentenyl, cyclopentadienyl,cyclohexenyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, cycloheptenyl,cycloheptatrienyl, cyclooctenyl, 1,5-cyclooctadienyl, cyclooctetraenyl,cyclononenyl or cyclodecenyl.

[0156] The cycloalkyl or cycloalkenyl radicals may comprise one or moresubstituents (preferably from 1 to 3) selected, for example, from amonghalogens such as chlorine, fluorine or bromine; cyano; nitro; amino;C₁-C₄ alkylamino; C₁-C₄ dialkylamino; C₁-C₄ alkyl; C₁-C₄ alkoxy;hydroxyl; they may also comprise from 1 to 3 heteroatoms such as sulfur,oxygen or nitrogen whose free valencies may be saturated with a hydrogenor a C₁-C₄ alkyl radical.

[0157] The bicycloalkyl or bicycloalkenyl groups are selected, forexample, from among bicyclic terpenes such as pinane, bornane, pinene orcamphor or adamantane derivatives.

[0158] The aryl groups are preferably selected from phenyl or naphthylrings, which may comprise one or more substituents (preferably from 1 to3) selected for example from halogen such as chlorine, fluorine orbromine; cyano; nitro; amino; C₁-C₄ alkylamino; C₁-C₄ dialkylamino;C₁-C₄ alkyl; C₁-C₄ alkoxy; hydroxyl. Phenyl, methoxyphenyl, naphthyl andthienyl are more particularly preferred.

[0159] The heteroaryl groups comprise in general one or more heteroatomsselected from among sulfur, oxygen or nitrogen.

[0160] The water-solubilizing groups are for example carboxyl andsulfoxy residues, and more particular their salts with physiologicallyacceptable cations such as alkali metal salts or trialkylammonium saltssuch as tri(hydroxyalkyl)ammonium or 2-methylpropan-1-ol-2-ammoniumsalts. There may also be mentioned ammonium groups such asalkylammoniums and their salified forms with physiologically acceptableanions.

[0161] The compounds of formula (I) are known per se and theirstructures and their syntheses are described in DE-1-9,755,649,EP-916,335, EP-1,133,980 and EP-1,133,981.

[0162] By way of example of a compound of formula (I), the following arerepresentative:

[0163] The preferred compounds of formula (I) are those in which: n=1 or2;

[0164] R¹ and R², which may be identical or different, are eachhydrogen, a C₁-C₂₀ alkyl radical, a C₁-C₁₂ alkoxy radical, a C₁-C₁₂monoalkylamino radical, a C₁-C₁₂ dialkylamino radical, awater-solubilizing substituent selected from among a carboxylate group,a sulfonate group or an ammonium residue;

[0165] R³ is a group COOR⁵, COR⁵, CONR⁵R⁶, a C₁-C₂₀ alkyl radical, aC₃-C₁₀ cycloalkyl radical, a C₃-C₁₀ cycloalkenyl radical, a C₇-C₁₀bicycloalkyl radical, optionally substituted phenyl, naphthyl orthienyl;

[0166] R⁴ is a group COOR⁶, COR⁶, CONR⁵R⁶, a C₁-C₂₀ alkyl radical, aC₃-C₆ cycloalkyl radical, a C₃-C₁₀ cycloalkenyl radical, a C₇-C₁₀bicycloalkyl radical, optionally substituted phenyl, naphthyl orthienyl;

[0167] the radicals R⁵ and R⁶, which may be identical or different, areeach hydrogen, a C₁-C₁₂ alkyl radical, a C₃-C₁₀ cycloalkyl radical, aC₃-C₁₀ cycloalkenyl radical, a C₇-C₁₀ bicycloalkyl radical, a C₃-C₁₀bicycloalkenyl radical, optionally substituted phenyl or naphthyl.

[0168] Among these compounds, there are more particularly preferredthose in which:

[0169] R¹ and R², which may be identical or different, are eachhydrogen, a C₁-C₂₀ alkyl radical, a C₁-C₂₀ alkoxy radical, awater-solubilizing substituent selected from among a carboxylate group,a sulfonate group or an ammonium residue;

[0170] R³ is a group COOR⁵, COR⁵, CONR⁵R⁶;

[0171] R⁴ is a group COOR⁶, COR⁶, CONR⁵R⁶;

[0172] the radicals R⁵ and R⁶, which may be identical or different, areeach hydrogen, a C₁-C₁₂ alkyl radical, a C₃-C₆ cycloalkyl radical, aC₃-C₁₀ cycloalkenyl radical, a C₇-C₁₀ bicycloalkyl radical, a C₃-C₁₀bicycloalkenyl radical, optionally substituted phenyl or naphthyl.

[0173] According to a particularly preferred embodiment, the compoundsof formula (I) are selected from among those of the following formula(I′):

[0174] wherein the radicals R⁵ and R⁶, which may be identical ordifferent, are each hydrogen, a C₁-C₂₀ alkyl radical, a C₃-C₆ cycloalkylradical, a C₃-C₁₀ cycloalkenyl radical.

[0175] Among these compounds of formula (I′), there may be mentioned,more particularly,1,1-dicarboxy(2,2′-dimethylpropyl)-4,4-diphenylbutadiene having thestructure:

[0176] Another 4,4-diarylbutadiene family which may formulated into theemulsions according to the invention are those corresponding to thefollowing formula (II):

[0177] in which the diene system is of the Z,Z; Z,E; E,Z or E,Econfiguration or mixtures of the said configurations and wherein:

[0178] R¹, R², R³ and n have the same meanings indicated in thepreceding formula (I);

[0179] Y′ is a group —O— or —NR⁹—;

[0180] R⁹ is hydrogen, a linear or branched C₁-C₂₀ alkyl radical, aC₂-C₁₀ alkenyl radical, a C₃-C₁₀ cycloalkyl radical, a C₇-C₁₀bicycloalkyl radical, a C₃-C₁₀ cycloalkenyl radical, a C₇-C₁₀bicycloalkenyl radical, an aryl radical, a heteroaryl radical;

[0181] X′ is a residue of a linear or branched, aliphatic orcycloaliphatic C₂-C₂₀ polyol comprising from 2 to 10 hydroxyl groups andhaving the valency q; with the proviso that the carbon chain of the saidresidue may be interrupted by one or more sulfur or oxygen atoms, one ormore imine groups, one or more C₁-C₄ alkylimino groups;

[0182] q ranges from 2 to 10; and

[0183] X′ is a C₂-C₂₀ polyol residue containing from 2 to 10 hydroxylgroups, and in particular:

[0184] The more preferred compounds of formula (II) are those in which:R¹ and R², which may be identical or different, are each hydrogen, aC₁-C₁₂ alkyl radical, a C₁-C₈ alkoxy radical, a water-solubilizingsubstituent selected from among a carboxylate group, a sulfonate groupor an ammonium residue;

[0185] R³ is a group COOR⁵, CONR⁵R⁶, CN, a C₃-C₁₀ cycloalkyl radical, aC₇-C₁₀ bicycloalkyl radical;

[0186] R⁵ and R⁶, which may be identical or different, are each a linearor branched C₁-C₂₀ alkyl radical, a C₃-C₁₀ cycloalkyl radical, a C₇-C₁₀bicycloalkyl radical, optionally substituted naphthyl or phenyl;

[0187] X′ is a C₂-C₂₀ polyol residue comprising from 2 to 6 hydroxylgroups and more particularly from 2 to 4.

[0188] The even more preferred compounds of formula (II) are those inwhich: X′ is an ethanol or pentaerythritol residue.

[0189] The even more particularly preferred compounds of formula (II)are selected from among:

[0190] The compounds of formula (II) as defined above are known per seand their structures and their syntheses are described inEP-A-1,008,586.

[0191] The 4,4-diarylbutadiene compounds are preferably present in thecomposition in proportions ranging from 0.1% to 20% by weight, morepreferably from 1% to 10% by weight relative to the total weight of thecomposition.

[0192] The compositions according to the invention may be provided inany of the galenic forms containing a fatty phase and an aqueous phasewhich are conventionally used for topical application and in particularin the form of dispersions of the lotion or serum type, emulsions havinga liquid or semi-liquid consistency of the milk type, which are obtainedby dispersing a fatty phase in an aqueous phase (O/W) or conversely(W/O), suspensions or emulsions having a soft, semi-solid or solidconsistency of the cream or gel type, or alternatively multipleemulsions (W/O/W or O/W/O), microemulsions, vesicular dispersions of theionic and/or nonionic type, or wax/aqueous phase dispersions. Thesecompositions are prepared according to the customary methods.

[0193] According to a particular embodiment of the invention, theoil-in-water or water-in-oil emulsions prepared with the AMPS polymersand/or copolymers according to the invention may contain only 1% byweight or less, and may even be free of emulsifying surfactants, whilebeing stable during storage.

[0194] The nature of the fatty phase entering into the composition ofthe emulsions according to the invention is not critical and it may thuscomprise all the compounds which are already known in general as beingsuitable for the manufacture of emulsions. In particular, thesecompounds may be selected, alone or as mixtures, from various fattysubstances, oils of plant, animal or mineral origin, natural orsynthetic waxes, and the like.

[0195] Among the oils which may be formulated into the composition ofthe fatty phase, there may be mentioned in particular:

[0196] mineral oils such as paraffin oil and liquid paraffin,

[0197] oils of animal origin, such as perhydrosqualene,

[0198] oils of plant origin, such as sweet almond oil, avocado oil,castor oil, olive oil, jojoba oil, sesame oil, groundnut oil, grape seedoil, rapeseed oil, copra oil, hazelnut oil, shea butter, palm oil,apricot kernel oil, calophyllum oil, rice bran oil, maize germ oil,wheat germ oil, soya bean oil, sunflower oil, evening primrose oil,safflower oil, passion flower oil and rye oil,

[0199] synthetic oils, such as purcellin oil, esters, such as forexample butyl myristate, isopropyl myristate, cetyl myristate, isopropylpalmitate, isopropyl adipate, ethylhexyl adipate, butyl stearate,hexadecyl stearate, isopropyl stearate, octyl stearate, isocetylstearate, decyl oleate, hexyl laurate, propylene glycol dicaprylate andesters derived from lanolic acid such as isopropyl lanolate, isocetyllanolate, isoparaffins and poly-α-olefins.

[0200] As other oils which can be formulated into the emulsionsaccording to the invention, there may also be mentioned C12-C15 fattyalcohol benzoates (Finsolv TN from FINETEX), ethers, lipophilic aminoacid derivatives such as isopropyl N-lauroylsarcosinate (Eldew SL-205from Ajinomoto), fatty alcohols such as lauryl, cetyl, myristyl,stearyl, palmityl or oleyl alcohol and 2-octyldodecanol,acetylglycerides, octanoates and decanoates of alcohols and polyalcoholssuch as those of glycol and of glycerol, ricinoleates of alcohols andpolyalcohols such as those of cetyl, fatty acid triglycerides such ascaprylic/capric triglycerides, C10-C18 saturated fatty acidtriglycerides, fluorinated and perfluorinated oils, lanolin,hydrogenated lanolin, acetylated lanolin and finally volatile ornonvolatile silicone oils.

[0201] Of course, the fatty phase may also contain one or moreconventional lipophilic cosmetic adjuvants, such as for example waxes,lipophilic gelling agents, surfactants, organic or inorganic particles,and in particular those which are already customarily used in themanufacture and production of anti-sun cosmetic compositions.

[0202] Conventionally, the dispersive aqueous phase may comprise water,or a mixture of water and polyhydric alcohol(s) such as for exampleglycerol, butylene glycol, propylene glycol and sorbitol, oralternatively a mixture of water and water-soluble lower alcohol(s) suchas ethanol, isopropanol or butanol (aqueous-alcoholic solution).

[0203] The compositions in accordance with the invention may furthercomprise other additional organic or inorganic UV-screening agents whichare active in UV-A and/or UV-B, which are water-soluble or fat-solubleor alternatively insoluble in the commonly-used cosmetic solvents.

[0204] The additional organic screening agents are selected inparticular from among anthranilates; cinnamic derivatives;dibenzoylmethane derivatives; salicylic derivatives, camphorderivatives; triazine derivatives such as those described in U.S. Pat.No. 4,367,390, EP-863,145, EP-517,104, EP-570,838, EP-796,851,EP-775,698, EP-878,469, EP-933,376, EP-507,691, EP-507,692, EP-790,243and EP-944,624; benzophenone derivatives; β,β-diphenyl acrylatederivatives; benzotriazole derivatives; benzalmalonate derivatives;benzimidazole derivatives; imidazolines; p-aminobenzoic acid (PABA)derivatives, benzoxazol derivatives as described in EP-0-832,642,E-1,027,883, E-1,300,137 and DE-1-0,162,844; bis-benzoazolyl derivativesas described in EP-669,323 and U.S. Pat. No.2,463,264; p-aminobenzoicacid (PABA) derivatives; methylenebis(hydroxyphenylbenzotriazole)derivatives as described in U.S. Pat. Nos. 5,237,071, 5,166,355,GB-2,303,549, DE-197-26-184 and EP-893,119; screening polymers andscreening silicones such as those described in particular in WO93/04665; dimers derived from α-alkylstyrene such as those described inDE-198-55-649 and mixtures thereof.

[0205] As examples of organic screening agents which are active in theUV-A and/or UV-B regions, there may be mentioned those designated belowunder their INCI names:

[0206] Para-Aminobenzoic Acid Derivatives:

[0207] PABA,

[0208] Ethyl PABA,

[0209] Ethyl Dihydroxypropyl PABA,

[0210] Ethylhexyl Dimethyl PABA sold in particular under the name“ESCALOL 507” by ISP,

[0211] Glyceryl PABA,

[0212] PEG-25 PABA sold under the name “UVINUL P25” by BASF,

[0213] Salicylic Derivatives:

[0214] Homosalate sold under the name “Eusolex HMS” by Rona/EMIndustries,

[0215] Ethylhexyl Salicylate sold under the name “NEO HELIOPAN OS” byHaarmann and REIMER,

[0216] Dipropyleneglycol Salicylate sold under the name “DIPSAL” bySCHER,

[0217] TEA Salicylate, sold under the name “NEO HELIOPAN TS” by Haarmannand REIMER,

[0218] Dibenzoylmethane Derivatives:

[0219] Butyl Methoxydibenzoylmethane sold in particular under thetrademark “PARSOL 1789” by HOFFMANN LA ROCHE,

[0220] Isopropyl Dibenzoylmethane,

[0221] Cinnamic Derivatives:

[0222] Ethylhexyl Methoxycinnamate sold in particular under thetrademark “PARSOL MCX” by HOFFMANN LA ROCHE,

[0223] Isopropyl Methoxy cinnamate,

[0224] Isoamyl Methoxy cinnamate sold under the trademark “NEO HELIOPANE 1000” by HAARMANN and REIMER,

[0225] Cinoxate,

[0226] DEA Methoxycinnamate,

[0227] Diisopropyl Methylcinnamate,

[0228] Glyceryl Ethylhexanoate Dimethoxycinnamate,

[0229] β,β′-Diphenyl Acrylate Derivatives:

[0230] Octocrylene sold in particular under the trademark “UVINUL N539”by BASF,

[0231] Etocrylene, sold in particular under the trademark “UVINUL N35”by BASF,

[0232] Benzophenone Derivatives:

[0233] Benzophenone-1 sold under the trademark “UVINUL 400” by BASF,

[0234] Benzophenone-2 sold under the trademark “UVINUL D50” by BASF,

[0235] Benzophenone-3 or Oxybenzone, sold under the trademark “UVINULM40” by BASF,

[0236] Benzophenone-4 sold under the trademark “UVINUL MS40” by BASF,

[0237] Benzophenone-5,

[0238] Benzophenone-6 sold under the trademark “Helisorb 11” by Norquay,

[0239] Benzophenone-8 sold under the trademark “Spectra-Sorb UV-24” byAmerican Cyanamid,

[0240] Benzophenone-9 sold under the trademark “UVINUL DS-49” by BASF,

[0241] Benzophenone- 12,

[0242] n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,

[0243] Benzylidenecamphor Derivatives:

[0244] 3-Benzylidene camphor manufactured under the name “MEXORYL SD” byCHIMEX,

[0245] 4-Methylbenzylidene camphor sold under the name “EUSOLEX 6300” byMERCK,

[0246] Benzylidene Camphor Sulfonic Acid manufactured under the name“MEXORYL SL” by CHIMEX,

[0247] Camphor Benzalkonium Methosulfate manufactured under the name“MEXORYL SO” by CHIMEX,

[0248] Terephthalylidene Dicamphor Sulfonic Acid manufactured under thename “MESORYL SX” by CHIMEX,

[0249] Polyacrylamidomethyl Benzylidene Camphor manufactured under thename “MESORYL SW” by CHIMEX,

[0250] Benzimidazole Derivatives:

[0251] Phenylbenzimidazole Sulfonic Acid sold in particular under thetrademark “EUSOLEX 232” by MERCK,

[0252] Disodium Phenyl Dibenzimidazole Tetra-sulfonate sold under thetrademark “NEO HELIOPAN AP” by Haarmann and REIMER,

[0253] Triazine Derivatives:

[0254] Anisotriazine sold under the trademark “TINOSORB S” by CIBASPECIALTY CHEMICALS,

[0255] Ethylhexyl triazone sold in particular under the trademark“UVINUL T150” by BASF,

[0256] Diethylhexyl Butamido Triazone sold under the trademark “UV-ASORBHEB” by SIGMA 3V,

[0257] 2,4,6-Tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine,

[0258] Benzotriazole Derivatives:

[0259] Drometrizole Trisiloxane sold under the name “Silatrizole” byRHODIA CHIMIE,

[0260] Methylene bis-Benzotriazolyl Tetramethylbutylphenol, sold insolid form under the trademark “MIXXIM BB/100” by FAIRMOUNT CHEMICAL orin micronized form in aqueous dispersion under the trademark “TINOSORBM” by CIBA SPECIALTY CHEMICALS,

[0261] Anthranilic Derivatives:

[0262] Menthyl anthranilate sold under the trademark “NEO HELIOPAN MA”by Haarmann and REIMER,

[0263] Imidazoline Derivatives:

[0264] Ethylhexyl Dimethoxybenzylidene Dioxoimidazoline Propionate,

[0265] Benzalmalonate Derivatives:

[0266] Polyorganosiloxane with benzalmalonate functional groups such aspolysilicone-15 sold under the trademark “PARSOL SLX” by HOFFMANNLAROCHE

[0267] Benzoxazole Derivatives:

[0268]2,4-Bis[5-1-(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazinesold under the name Uvasorb K2A by Sigma 3V;

[0269] and mixtures thereof.

[0270] The organic screening agents which are more particularlypreferred are selected from among the following compounds:

[0271] Ethylhexyl Salicylate,

[0272] Ethylhexyl Methoxycinnamate,

[0273] Octocrylene,

[0274] Butyl Methoxydibenzoylmethane,

[0275] Phenylbenzimidazole Sulfonic Acid,

[0276] Benzophenone-3,

[0277] Benzophenone-4,

[0278] Benzophenone-5,

[0279] n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,

[0280] 4-Methylbenzylidene camphor,

[0281] Terephthalylidene Dicamphor Sulfonic Acid,

[0282] Disodium Phenyl Dibenzimidazole Tetra-sulfonate,

[0283] 2,4,6-Tris(diisobutyl 4′-aminobenzalmalonate)-s-triazine,

[0284] Anisotriazine,

[0285] Ethylhexyl triazone,

[0286] Diethylhexyl Butamido Triazone,

[0287] Methylene bis-Benzotriazolyl Tetramethylbutylphenol,

[0288] Drometrizole Trisiloxane,

[0289] Polysilicone 15,

[0290]2,4-Bis-[5-1-(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine

[0291] and mixtures thereof.

[0292] The additional inorganic screening agents are selected from amongpigments or nanopigments (average size of the primary particles:generally between 5 nm and 100 nm, preferably between 10 nm and 50 nm)of metal oxides, coated or uncoated, such as for example nanopigments oftitanium oxide (amorphous or crystallized in rutile and/or anataseform), iron oxide, zinc oxide, zirconium oxide or cerium oxide which areall UV photoprotective agents well known per se. Conventional coatingagents are moreover alumina and/or aluminum stearate. Such nanopigmentsof metal oxides, coated or uncoated, are described in particular inEP-518,772 and E-518,773.

[0293] The additional screening agents according to the invention aregenerally present in the compositions according to the invention in anamount ranging from 0.1% to 30% by weight, and preferably from 0.5% to15% by weight, relative to the total weight of the composition.

[0294] The compositions according to the invention may also containagents for artificially bronzing and/or tanning the skin (self-tanningagents).

[0295] The self-tanning agents are generally selected from among mono-or polycarbonylated compounds such as for example isatin, alloxan,ninhydrin, glyceraldehyde, mesotartaric aldehyde, glutaraldehyde,erythrulose, derivatives of 4,5-pyrazolindiones as described inFR-2,466,492 and WO 97/35842, dihydroxyacetone (DHA),4,4-dihydroxypyrazolin-5-one derivatives as described in EP-903,342. DHAwill preferably be used.

[0296] DHA may be used in free form and/or encapsulated for example intolipid vesicles such as liposomes, which are described in particular inWO 97/25970.

[0297] The mono- or polycarbonylated self-tanning agents are generallypresent in the compositions according to the invention in proportionsranging from 0.1% to 10% by weight relative to the total weight of thecomposition, and preferably from 0.2% to 8% by weight relative to thetotal weight of the composition.

[0298] The compositions in accordance with the present invention mayadditionally comprise conventional cosmetic adjuvants, selected inparticular from among organic solvents, ionic or nonionic thickeners,demulcents, humectants, opacifying agents, stabilizers, emollients,silicones, insect repellents, perfumes, preservatives, surfactants,fillers, active agents, pigments, polymers, propellants, alkanizing oracidifying agents or any other ingredient customarily used in thecosmetic and/or dermatological field.

[0299] Of course, one skilled in this art will be careful to choose thepossible additional compound(s) cited above and/or their quantities suchthat the advantageous properties intrinsically attached to thecompositions in accordance with the invention are not, or notsubstantially, impaired by the addition(s) envisaged.

[0300] Among the organic solvents lower alcohols and polyols may bementioned.

[0301] Among the thickeners, there may be mentioned crosslinked acrylicpolymers such as the Carbomers provided by Noveon, acrylate/C10-30 alkylacrylate crosslinked polymers of the Pemulen type provided by Noveon orpolyacrylate-3 sold under the name Viscophobe DB 1000 by Amerchol);polymers derived from acrylamido-2-methylpropanesulfonic acid(Hostacerin AMPS provided by Clariant, Sepigel 305 provided by SEPPIC),synthetic neutral polymers such as poly-N-vinylpyrrolidone,polysaccharides such as guar and xanthan gums, and modified orunmodified cellulose derivatives such as hydroxypropylated guar gum,methylhydroxyethylcellulose and hydroxypropylmethylcellulose.

[0302] The compositions according to the invention find application in alarge number of treatments, in particular cosmetic treatments, of theskin, the lips and the hair, including the scalp, in particular for theprotection and/or care of the skin, the lips and/or the hair, and/or formaking up the skin and/or the lips.

[0303] The present invention also features the use of the compositionsaccording to the invention as defined above for the manufacture ofproducts for the cosmetic treatment of the skin, the lips and the hair,including the scalp, in particular for the protection and/or care of theskin, the lips and/or the hair, and/or for making up the skin and/or thelips.

[0304] The cosmetic compositions according to the invention may forexample be used as care and/or sun protection product for the faceand/or the body, having a liquid or semi-liquid consistency, such asmilks, more or less unctuous creams, gel creams, pastes. They may beoptionally packaged as an aerosol and provided in the form of a mousseor a spray.

[0305] The compositions according to the invention in the form ofvaporizable fluid lotions in accordance with the invention are appliedto the skin or the hair in the form of fine particles by means ofpressurized devices. The devices in accordance with the invention arewell known to persons skilled in the art and comprise nonaerosol pumpsor “atomizers”, the aerosol containers comprising a propellant andaerosol pumps using compressed air as propellant. The latter aredescribed in U.S. Pat. Nos. 4,077,441 and 4,850,517.

[0306] The compositions packaged as an aerosol in accordance with theinvention contain in general conventional propellants such as, forexample, the hydrofluorinated compounds dichlorodifluoromethane,difluoroethane, dimethyl ether, isobutane, n-butane, propane,trichlorofluoromethane. They are preferably present in quantitiesranging from 15 to 50% by weight relative to the total weight of thecomposition.

[0307] In order to further illustrate the present invention and theadvantages thereof, the following specific examples are given, it beingunderstood that same are intended only as illustrative and in nowiselimitative. In said examples to follow, all parts and percentages aregiven by weight, unless otherwise indicated.

EXAMPLES Example A Moisturizing and Photoprotective Creams (O/WEmulsions Stabilized with Surfactants and Comprising a CrosslinkedGelling Copolymer Derived from AMPS)

[0308] Emulsion 1 (not in accordance with the Emulsion 2 Ingredientsinvention) (invention) Mixture of glyceryl monostearate and 2.5 2.5polyethylene glycol stearate (100 EO) 50/50 Polyethylene glycolmonostearate (50 EO) 2.5 2.5 Stearyl alcohol 0.5 0.5 Octylmethoxycinnamate 7 7 1,1-dicarboxy-(2′2′-dimethylpropyl)-4,4- 0 5diphenylbutadiene (compound f) C₁₂₋₁₅ alkyl benzoate 10 10 Glycerin 3 33,3′-terephthalylidene-10,10′- 5 0 dicamphorsulfonic acid Ammoniumpolyacryldimethyltauramide 1 1 (HOSTACERIN AMPS) Triethanolamine 3.550.01 Preservative 0.3 0.3 Water qs 100 qs 100 Viscosity (Pa · s) under200 s⁻¹ (Rheomat 0.16 4.7 180)

[0309] Mode of Preparation:

[0310] The surfactants and optionally the diarylbutadiene derivative aresolubilized at 75° C. in the oily phase with stirring; the solutionobtained is macroscopically homogeneous. Each emulsion is prepared byslowly introducing the oily phase into the aqueous phase with stirringwith the aid of a Moritz-type homogenizer at 70° C. at a stirring speedof 2,000 rpm for 15 minutes. Each emulsion is then cooled to roomtemperature with gentle stirring.

[0311] After 24 hours at room temperature, it is observed that theemulsion 1 becomes liquid while the emulsion 2 according to theinvention is in the form of a stable, brilliant cream which is pleasantto apply to the skin.

Example B Photoprotective Milks (Surfactant-Free O/W EmulsionsStabilized with a Non-Crosslinked Amphiphilic Copolymer Derived fromAMPS)

[0312] Emulsion 3 (not in accordance with the Emulsion 4 Ingredientsinvention) (invention) Octyl methoxycinnamate 7 71,1-dicarboxy-(2′2′-dimethylpropyl)-4,4- 0 5 diphenylbutadiene (compoundf) C₁₂₋₁₅ alkyl benzoate 10 10 Glycerin 3 33,3′-terephthalylidene-10,10′- 5 0 dicamphorsulfonic acidNon-crosslinked copolymer of AMPS and an 0.5 0.5 ester of (meth)acrylicacid and a polyoxyethylenated C₁₆-C₁₈ fatty alcohol containing 8 EO(GENAPOL T-080) such as that described in example 7 of applicationEP1059142 Triethanolamine 3.55 0.01 Preservative 0.3 0.3 Water qs 100 qs100 Viscosity (Pa · s) under 200 s⁻¹ (Rheomat 0.04 0.15 180)

[0313] Mode of Preparation:

[0314] The amphiphilic AMPS copolymer is solubilized for 2 hours, withstirring, in the aqueous phase at 25° C.; the solution obtained ismacroscopically homogeneous. The emulsion is prepared by slowlyintroducing the oily phase into the aqueous phase with stirring with theaid of a Moritz-type homogenizer at a stirring speed of 2,000 rpm for 15minutes.

[0315] The emulsion 3 becomes fluid and loses its viscosity. Theemulsion 4 according to the invention remains stable and has a nicemilk-type texture.

Example C Photoprotective Creams (Surfactant-Free O/W EmulsionsStabilized with an Amphiphilic Copolymer Derived from Crosslinked AMPS)

[0316] Emulsion 5 (not in accordance with the Emulsion 6 Ingredientsinvention) (invention) Octyl methoxycinnamate 7 71,1-dicarboxy-(2′2′-dimethylpropyl)-4,4- 0 5 diphenylbutadiene (compoundf) C₁₂₋₁₅ alkyl benzoate 10 10 Glycerin 3 33,3′-terephthalylidene-10,10′- 5 0 dicamphorsulfonic acid Crosslinkedcopolymer of AMPS and an 0.5 0.5 ester of (meth)acrylic acid and apolyoxyethylenated C₁₆-C₁₈ fatty alcohol containing 25 EO (GENAPOLT-250) such as that described in example 3 of application EP1059142Triethanolamine 3.55 0.01 Preservative 0.3 0.3 Water qs 100 qs 100Viscosity (Pa · s) under 200 s⁻¹ (Rheomat 0.05 0.70 180)

[0317] Mode of Preparation:

[0318] The amphiphilic AMPS copolymer is solubilized for 2 hours, withstirring, in the aqueous phase at 25° C.; the solution obtained ismacroscopically homogeneous. Each emulsion is prepared by slowlyintroducing the oily phase into the aqueous phase with stirring with theaid of a Moritz-type homogenizer at a stirring speed of 2,000 rpm for 15minutes.

[0319] The emulsion 5 becomes macroscopically destabilized after 24hours at room temperature, with the appearance of a phenomenon ofcreaming. The emulsion 6 remains stable and has a nice milk-typetexture.

[0320] Each patent, patent application, publication and literaturearticle/report cited or indicated herein is hereby expresslyincorporated by reference.

[0321] While the invention has been described in terms of variousspecific and preferred embodiments, the skilled artisan will appreciatethat various modifications, substitutions, omissions, and changes may bemade without departing from the spirit thereof. Accordingly, it isintended that the scope of the present invention be limited solely bythe scope of the following claims, including equivalents thereof.

What is claimed is:
 1. A photoprotective composition comprising at leastone aqueous phase, at least one oily phase, at least one partially orcompletely neutralized, crosslinked or non-crosslinked water-soluble orwater-dispersible acrylamido-2-methylpropanesulfonic acid (AMPS) polymerand at least one UV radiation-screening system, said at least onescreening system comprising at least one 4,4-diarylbutadieneUV-A-screening agent.
 2. The photoprotective composition as defined byclaim 1, said at least one AMPS polymer being partially or completelyneutralized with an inorganic or organic base.
 3. The photoprotectivecomposition as defined by claim 2, such neutralization being with sodiumhydroxide, potassium hydroxide or aqueous ammonia.
 4. Thephotoprotective composition as defined by claim 2, such neutralizationbeing with mono-, di- or triethanolamine, aminomethylpropanediol,N-methylglucamine, basic amino acids and mixtures thereof.
 5. Thephotoprotective composition as defined by claim 1, said at least oneAMPS polymer being at least 90% neutralized.
 6. The photoprotectivecomposition as defined by claim 1, said at least one AMPS polymer beingcrosslinked with a crosslinking agent selected from among olefinicallypolyunsaturated compounds.
 7. The photoprotective composition as definedby claim 6, said crosslinking agent being selected from amongdivinylbenzene, diallyl ether, dipropylene glycol diallyl ether,polyglycol diallyl ethers, triethylene glycol divinyl ether,hydroquinone diallyl ether, ethylene glycol or tetraethylene glycoldi(meth)acrylate, trimethylolpropane triacrylate,methylenebisacrylamide, methylenebismethacrylamide, triallylamine,triallyl cyanurate, diallyl maleate, tetraallylethylenediamine,tetraallyloxyethane, trimethylolpropane diallyl ether,allyl(meth)acrylate, allyl ethers of alcohols of the sugar series, orother allyl or vinyl ethers of polyfunctional alcohols, and the allylesters of phosphoric and/or vinylphosphonic acid derivatives, ormixtures thereof.
 8. The photoprotective composition as defined by claim6, said crosslinking agent comprising methylenebisacrylamide, allylmethacrylate or trimethylolpropane triacrylate (TMPTA).
 9. Thephotoprotective composition as defined by claim 1, the degree ofcrosslinking ranging from 0.01 to 10 mol % relative to the polymer. 10.The photoprotective composition as defined by claim 1, said at least oneAMPS polymer being water-soluble or water-dispersible and selected fromthe group consisting of: (i) crosslinked or non-crosslinked AMPShomopolymers; (ii) crosslinked or non-crosslinked copolymers obtainedfrom AMPS and from one or more hydrophilic ethylenically unsaturatedmonomers or hydrophobic ethylenically unsaturated monomers containing nofatty chain.
 11. The photoprotective composition as defined by claim 10,said water-dispersible AMPS polymers having a molar mass ranging from50,000 g/mol to 10,000,000 g/mol.
 12. The photoprotective composition asdefined by claim 10, the AMPS homopolymer comprising ammoniumpolyacryloyldimethyltauramide.
 13. The photoprotective composition asdefined by claim 10, the crosslinked or non-crosslinked copolymers ofAMPS and of one or more hydrophilic or hydrophobic ethylenicallyunsaturated monomers being selected from among: (a) copolymers of AMPSand acrylamide or methylacrylamide; (b) copolymers of AMPS andvinylpyrrolidone or vinylformamide.
 14. The photoprotective compositionas defined by claim 13, the water-dispersible copolymer of AMPS beingselected from among: polyacrylamide/C₁₃-C₁₄ isoparaffin/laureth-7;acrylamide/sodium acryloyldimethyltaurate/isohexadecane/polysorbate-80;ammonium acryloyldimethyltaurate/VP copolymer.
 15. The photoprotectivecomposition as defined by claim 1, said at least one AMPS polymer beingamphiphilic.
 16. The photoprotective composition as defined by claim 15,said amphiphilic AMPS polymer comprising at least one fatty chaincontaining from 7 to 30 carbon atoms.
 17. The photoprotectivecomposition as defined by claim 15, said amphiphilic AMPS polymer havinga weight-average molecular weight ranging from 50,000 to 10,000,000. 18.The photoprotective composition as defined by claim 15, said amphiphilicAMPS polymer comprising a random amphiphilic AMPS polymer modified byreaction with a C₆-C₂₂ n-monoalkylamine or di-n-alkylamine andoptionally containing one or more ethylenically unsaturated hydrophilicmonomers.
 19. The photoprotective composition as defined by claim 15,said amphiphilic AMPS polymer being selected from among AMPS polymersfrom at least one ethylenically unsaturated monomer containing at leastone hydrophobic part having from 7 to 30 carbon atoms and optionally oneor more ethylenically unsaturated hydrophilic comonomers.
 20. Thephotoprotective composition as defined by claim 19, said ethylenicallyunsaturated monomers containing at least one hydrophobic part havingfrom 7 to 30 carbon atoms being selected from among acrylates andacrylamides of the following formula (1):

in which R₂₇ is a hydrogen atom, a linear or branched C₁-C₆ alkylradical; Y is O or NH; and R₂₈ is a hydrophobic radical containing afatty chain having from 7 to 22 carbon atoms.
 21. The photoprotectivecomposition as defined by claim 20, wherein formula (1), the hydrophobicradical R₂₈ is a saturated or unsaturated, linear or branched C₇-C₁₈alkyl radical, C₇-C₁₈ perfluorinated alkyl radical, the cholesterylradical or a cholesterol ester, or an aromatic polycyclic radical. 22.The photoprotective composition as defined by claim 20, wherein formula(1), the hydrophobic radical R₁₈ further contains at least one alkyleneoxide structural unit.
 23. The photoprotective composition as defined byclaim 22, the number of moles of oxyalkylenated structural units rangingfrom 1 to 30 mol.
 24. The photoprotective composition as defined byclaim 20, the amphiphilic AMPS polymers comprising amphiphiliccopolymers of: (a) 2-acrylamido-2-methylpropanesulfonic acid (AMPS)structural units of the following formula (2):

in which X⁺ is a proton, an alkali metal cation, an alkaline earth metalcation or the ammonium ion; and (b) structural units of the followingformula (3):

in which n and p, independently of each other, are each a number ofmoles and varies from 0 to 30, provided that n+p is less than or equalto 30; R₂₇ has the same meaning indicated above in formula (1) and R₂₉is a linear or branched alkyl containing m carbon atoms ranging from 7to
 22. 25. The photoprotective composition as defined by claim 24,wherein formula (2), X⁺ is sodium or ammonium.
 26. The photoprotectivecomposition as defined by claim 24, said amphiphilic AMPS polymerscomprising: (i) those which are non-crosslinked, in which p=0, n=7 or25, R₂₇ is methyl and R₂₉ is a mixture of C₁₂-C₁₄ or C₁₆-C₁₈ alkyl, or(ii) those which are crosslinked, in which p=0, n=8 or 25, R₂₇ is methyland R₂₉ is a mixture of C₁₆-C₁₈ alkyl.
 27. The photoprotectivecomposition as defined by claim 24, wherein the molar proportion ofstructural units of formula (3) ranges from 0.1 to 50%.
 28. Thephotoprotective composition as defined by claim 24, wherein the molarproportion of structural units of formula (3) ranges from 50.1% to99.9%.
 29. The photoprotective composition as defined by claim 1, saidat least one AMPS polymer comprising from 0.01% to 20% by weightrelative to the total weight of the composition.
 30. The photoprotectivecomposition as defined by claim 1, said at least one 4,4-diarylbutadieneUV-A-screening agent having the following formula (I):

in which the diene system is of the Z,Z; Z,E; E,Z or E,E configurationor mixture of said configurations, and wherein: R¹ and R², which may beidentical or different, are each hydrogen, a C₁-C₂₀ alkyl radical, aC₂-C₁₀ alkenyl radical, a C₁-C₁₂ alkoxy radical, a C₃-C₁₀ cycloalkylradical, a C₃-C₁₀ cycloalkenyl radical, a C₁-C₂₀ alkoxycarbonyl radical,a C₁-C₁₂ monoalkylamino radical, a C₁-C₁₂ dialkylamino radical, an arylradical, a heteroaryl radical or a water-solubilizing substituentselected from among a carboxylate residue, a sulfonate residue or anammonium residue; R³ is a group COOR⁵, COR⁵, CONR⁵R⁶, CN, O═S(—R⁵)═O,O═S(—OR⁵)═O, R⁷O—P—(—OR⁸)═O, a C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenylradical, a C₃-C₁₀ cycloalkyl radical, a C₇-C₁₀ bicycloalkyl radical, aC₃-C₁₀ cycloalkenyl radical, a C₇-C₁₀ bicycloalkenyl radical, anoptionally substituted C₆-C₁₈ aryl radical an optionally substitutedC₃-C₇ heteroaryl radical; R⁴ is a group COOR⁶, COR⁶, CONR⁵R⁶, CN,O═S(—R⁶)═O, O═S(—OR⁶)═O, R⁷O—P—(—OR⁸)═O, a C₁-C₂₀ alkyl radical, aC₂-C₁₀ alkenyl radical, a C₃-C₁₀ cycloalkyl radical, a C₇-C₁₀bicycloalkyl radical, a C₃-C₁₀ cycloalkenyl radical, a C₇-C₁₀bicycloalkenyl radical, an optionally substituted C₆-C₁₈ aryl radical,an optionally substituted C₃-C₇ heteroaryl radical; the radicals R⁵ toR⁸, which may be identical or different, are each hydrogen, a C₁-C₂₀alkyl radical, a C₂-C₁₀ alkenyl radical, a C₃-C₁₀ cycloalkyl radical, aC₇-C₁₀ bicycloalkyl radical, a C₃-C₁₀ bicycloalkenyl radical, a C₇-C₁₀cycloalkenyl radical, an optionally substituted aryl radical, anoptionally substituted heteroaryl radical; and n ranges from 1 to 3;with the proviso that the radicals R³ to R⁸ can together form, with thecarbon atoms from which they depend, a C₅-C₆ ring which may be fused.31. The photoprotective composition as defined by claim 30, whereinformula (I): n=1 or 2; R¹ and R², which may be identical or different,are each hydrogen, a C₁-C₂₀ alkyl radical, a C₁-C₁₂ alkoxy radical, aC₁-C₁₂ monoalkylamino radical, a C₁-C₁₂ dialkylamino radical, awater-solubilizing substituent selected from among a carboxylate group,a sulfonate group or an ammonium residue; R³ is a group COOR⁵, COR⁵,CONR⁵R⁶, a C₁-C₂₀ alkyl radical, a C₃-C₁₀ cycloalkyl radical, a C₃-C₁₀cycloalkenyl radical, a C₇-C₁₀ bicycloalkyl radical, optionallysubstituted phenyl, naphthyl or thienyl; R⁴ is a group COOR⁶, COR⁶,CONR⁵R⁶, a C₁-C₂₀ alkyl radical, a C₃-C₆ cycloalkyl radical, a C₃-C₁₀cycloalkenyl radical, a C₇-C₁₀ bicycloalkyl radical, optionallysubstituted phenyl, naphthyl or thienyl; and the radicals R⁵ and R⁶,which may be identical or different, are each hydrogen, a C₁-C₁₂ alkylradical, a C₃-C₁₀ cycloalkyl radical, a C₃-C₁₀ cycloalkenyl radical, aC₇-C₁₀ bicycloalkyl radical, a C₃-C₁₀ bicycloalkenyl radical, optionallysubstituted phenyl or naphthyl.
 32. The photoprotective composition asdefined by claim 31, wherein formula (I): R¹ and R², which may beidentical or different, are each hydrogen, a C₁-C₂₀ alkyl radical, aC₁-C₂₀ alkoxy radical, a water-solubilizing substituent selected fromamong a carboxylate group, a sulfonate group or an ammonium residue; R³is a group COOR⁵, COR⁵, CONR⁵R⁶; R⁴ is a group COOR⁶, COR⁶, CONR⁵R⁶; andthe radicals R⁵ and R⁶, which may be identical or different, are eachhydrogen, a C₁-C₁₂ alkyl radical, a C₃-C₆ cycloalkyl radical, a C₃-C₁₀cycloalkenyl radical, a C₇-C₁₀ bicycloalkyl radical, a C₃-C₁₀bicycloalkenyl radical, optionally substituted phenyl or naphthyl. 33.The photoprotective composition as defined by claim 32, the compound offormula (I) having the following formula (I′):

wherein the radicals R⁵ and R⁶, which may be identical or different, areeach hydrogen, a C₁-C₂₀ alkyl radical, a C₃-C₆ cycloalkyl radical, aC₃-C₁₀ cycloalkenyl radical.
 34. The photoprotective composition asdefined by claim 33, the compound of formula (I′) being1,1-dicarboxy(2′2′dimethylpropyl)-4,4-diphenylbutadiene having thestructure:


35. The photoprotective composition as defined by claim 1, said at leastone 4,4-diarylbutadiene UV-A-screening agent having the followingformula (II):

in which the diene system is of the Z,Z; Z,E; E,Z or E,E configurationor mixture of said configurations and wherein: R¹, R², R³ and n have themeanings indicated in the formula (I); Y′ is a group —O— or —NR⁹—; R⁹ ishydrogen, a linear or branched C₁-C₂₀ alkyl radical, a C₂-C₁₀ alkenylradical, a C₃-C₁₀ cycloalkyl radical, a C₇-C₁₀ bicycloalkyl radical, aC₃-C₁₀ cycloalkenyl radical, a C₇-C₁₀ bicycloalkenyl radical, an arylradical, a heteroaryl radical; X′ is a residue of a linear or branched,aliphatic or cycloaliphatic C₂-C₂₀ polyol comprising from 2 to 10hydroxyl groups and having the valency q; with the proviso that thecarbon chain of said residue may be interrupted by one or more sulfur oroxygen atoms, one or more imine groups, one or more C₁-C₄ alkyliminogroups; and q ranges from 2 to
 10. 36. The photoprotective compositionas defined by claim 35, wherein formula (II): R¹ and R², which may beidentical or different, are each hydrogen, a C₁-C₁₂ alkyl radical, aC₁-C₈ alkoxy radical, a water-solubilizing substituent selected fromamong a carboxylate group, a sulfonate group or an ammonium residue; R³is a group COOR⁵, CONR⁵R⁶, CN, a C₃-C₁₀ cycloalkyl radical, a C₇-C₁₀bicycloalkyl radical; R⁵ and R⁶, which may be identical or different,are each a linear or branched C₁-C₂₀ alkyl radical, a C₃-C₁₀ cycloalkylradical, a C₇-C₁₀ bicycloalkyl radical, optionally substituted naphthylor phenyl; and X′ is a C₂-C₂₀ polyol residue comprising from 2 to 6hydroxyl groups.
 37. The photoprotective composition as defined by claim36, wherein formula (II), X′ is an ethanol or pentaerythritol residue.38. The photoprotective composition as defined by claim 37, saidcompound of formula (II) being selected from among the followingcompounds:


39. The photoprotective composition as defined by claim 1, said at leastone 4,4-diarylbutadiene compound constituting from 0.1% to 20% by weightrelative to the total weight of the emulsion.
 40. The photoprotectivecomposition as defined by claim 1, further comprising at least oneadditional organic or inorganic sunscreening agent active in the UV-Aand/or UV-B regions, water-soluble, fat-soluble or insoluble in theusual cosmetic solvents.
 41. The photoprotective composition as definedby claim 40, comprising at least one additional organic screening agentselected from among the anthranilates; cinnamic derivatives;dibenzoylmethane derivatives; salicylic derivatives, camphorderivatives; triazine derivatives; benzophenone derivatives;β,β′-diphenyl acrylate derivatives; benzotriazole derivatives;benzalmalonate derivatives; benzimidazole derivatives; imidazolines;bis-benzoazolyl derivatives; p-aminobenzoic acid (PABA) derivatives;benzoxazole derivatives; methylenebis(hydroxyphenylbenzotriazole)derivatives; screening polymers and screening silicones; dimers derivedfrom α-alkylstyrene and mixtures thereof.
 42. The photoprotectivecomposition as defined by claim 41, said at least one additional organicscreening agent comprising: Ethylhexyl Salicylate, EthylhexylMethoxycinnamate, Octocrylene, Butyl Methoxydibenzoylmethane,Phenylbenzimidazole Sulfonic Acid, Benzophenone-3, Benzophenone-4,Benzophenone-5, n-Hexyl 2-(4-diethylamino-2-hydroxybenzoyl)benzoate,4-Methylbenzylidene camphor, Terephthalylidene Dicamphor Sulfonic acid,Disodium Phenyl Dibenzimidazole Tetra-sulfonate,2,4,6-Tris(4′-diisobutyl aminobenzalmalonate)-s-triazine, Anisotriazine,Ethylhexyl triazone, Diethylhexyl Butamido Triazone, Methylenebis-Benzotriazolyl Tetramethylbutylphenol, Drometrizole Trisiloxane,Polysilicone 15,2,4-Bis-[5-1-(dimethylpropyl)benzoxazol-2-yl-(4-phenyl)imino]-6-(2-ethylhexyl)imino-1,3,5-triazine,and mixtures thereof.
 43. The photoprotective composition as defined byclaim 40, comprising at least one additional inorganic screening agentselected from among pigments or nanopigments of metal oxides, whethercoated or uncoated.
 44. The photoprotective composition as defined byclaim 43, said at least one additional inorganic screening agentcomprising nanopigments of titanium oxide, which is amorphous orcrystallized, in rutile and/or anatase form, iron oxide, zinc oxide,zirconium oxide or cerium oxide.
 45. The photoprotective composition asdefined by claim 1, further comprising at least one agent for artificialbronzing and/or tanning of the skin.
 46. The photoprotective compositionas defined by claim 1, further comprising at least one cosmetic adjuvantselected from among organic solvents, ionic or nonionic thickeners,demulcents, humectants, opacifying agents, stabilizers, emollients,silicones, insect repellents, perfumes, preservatives, surfactants,fillers, active agents, pigments, polymers, propellants, alkalinizing oracidifying agents or any other ingredient commonly employed in thecosmetic and/or dermatological field.
 47. The photoprotectivecomposition as defined by claim 1, formulated as a dispersion of thelotion or serum type, an oil-in-water or water-in-oil emulsion, amultiple emulsion, a microemulsion, a vesicular dispersion of the ionicand/or nonionic type or a wax/aqueous phase dispersion.
 48. Thephotoprotective composition as defined by claim 1, formulated as anoil-in-water or water-in-oil emulsion containing at most 1% by weight ofemulsifying surfactant relative to the total weight of the composition.49. A method for the photoprotection of the skin, lips and/or hairagainst the damaging effects of UV-radiation, comprising topicallyapplying thereon, a thus effective amount of a photoprotectivecomposition comprising at least one aqueous phase, at least one oilyphase, at least one partially or completely neutralized, crosslinked ornon-crosslinked water-soluble or water-dispersibleacrylamido-2-methylpropanesulfonic acid (AMPS) polymer and at least oneUV radiation-screening system, said at least one screening systemcomprising at least one 4,4-diarylbutadiene UV-A-screening agent.